Method of and apparatus for conducting catalytic exothermic gaseous reactions



y 1, 19ml R. WILLIAMS 7 1,769,873

METHOD OF AND APPARATUS FOR CONDUCTING CATALYTIC EXOTHERMIC GASEOUS REACTIONS Filed Nov. 6 1925 6B ZINVENTOR ATTORNEYS Patented July 193$ WILL, OF WILMINGTON, DEMW F' wan - CORPORATION, OF WILMINGTON, DELAWA A CORYOBATIQN OF DELAWARE us roe coanncrme CATALIG nxornnamrc a one Application tiled November 6, 1825. Serial No. 67,382.

This invention relates to improved methods of and apparatus for efiecting exother serve mic gaseous reactions,and particularly for controlling such reactions to improve the eficiency thereof.

it is recognized that in carrying out catalytic exothermic gaseous reactions particularl those of the type which, lihe the synthesls'of ammonia and other syntheses employing hydrogen, are carried out under pressure, means must be provided for removing heat from the catalyst; otherwise the temperature of the catalyst will rapidly rise to value at which the physical form or activity of the catalyst may be unfavorably affected; the reaction equilibrium may be changed in such a way as to result in a lower conversion of the reacting gasesg and/or undesirable side reactions may be accelerated.

The problem of removal of heat from the catalyst is complicated by the fact that the evolution of heat is by no means uniform throughout the body of catalyst. it have obfor example, that in an apparatus for the synthesis of ammonia, in which the gases first contacted with the catalyst at a temperature of about 600 0., the tempera ture, during passage through the first 7 per cent of the catalyst tube,rose rapidly to a maximum of about 7 00 C. This temperature was substantially maintained through the next 15 per cent of the tube, but then fell ofi at a fairly constant rate until, on leaving. the catalyst, the temperature of the gases was only about 400 C. From the standpoint of temperature distribution the catalyst may, therefore, be considered as consisting of three zones: (1) a small zone in which the temperature rises; 2) a-somewhat larger zone in which a ma3or portion of the reaction occurs with the temperature rapidly increasing to a maximum; (3) .a comparatively large. zone in which the temperature falls and the conversion may be relatively small.

Assuming that the gases as they first con-- tact with the catalyst are not hot enough for the reaction to actively begin, as they flow in contact with the catalyst, the gases will at first react relatively slowly until the heat evolved has raised their temperature to a value at which the reaction will actively be gin. This point in the catalyst marks the end of the first zone. Now, if it is remembered that a rise in temperature increases the velocity but is unfavorable to the e uilibrium of an exothermic reaction, it w' be seen that in the next portions of the catalyst with which the gases contact the reaction will take place with evolution of heat and more and more rapidly until a balance is established between the temperature attained and the equilibrium conversion corresponding to that temperature, which may be high enough to result in one or more of the unfavorable conditions previously referred to. The second zone of the catalyst will, therefore, constitute a region of high temperature. Since the concentration of product in this zone has practically reached the limit set by the high temperature, conversion brought about y the balance of the catalyst will be limited by the extent to which the gases are allowed to cool in contact with 1t and are thus brought into regions where the equilibrium conditions are more favorable, However, the tendenc may be for the gases to cool too much, 1., e., below the temperature at which the catalyst is efiectively active; so that it may be that comparatively little conversion is effected in at least the latter part "of the third zone of catalyst. Thus, in the case of the example of ammonia synthesis operation described above, the temperature the catalyst tube, and this temperature ordi= narily is too low for eficient carrying out high temperature will be transferredto a succeeding portion, and so on. It will be seentthat thus the catalyst may all eventu- ASSIGNOR T0 DU MINT om was below 500 C. in the last 15 per cent of till this in turn becomes inactive, the zone of tee ' smaller amounts 0 which a suitable apparatus or efi'ectin the ally be rendered inactive and, as the process of deterioration oes on, progressively active catalyst will be available to the gases contacting therewith.

It has been proposed heretofore to remove a portion of the surplus heat in the gases leaving the reaction zone. Some of the heat is carried off by merely discharging the gases after the reaction is complete gases have, however, as above indicated, a much lower temperature than the catalyst at the point where the reaction is most active and are available, therefore, as a coolin medium for the catalyst.

- Tt is the object of the present invention to provide a method of and apparatus for utilizing the gaseous products of the reaction to cool the catalyst. in the most effective manner and to remove the maximum of surplus heat therefrom.

Other ob'ects and advantages of the invention wi be apparent as it is better understood by reference to the following specification and .accompanyin drawing in improvement indicated is illustrate diagrammatically.

I have discovered that the removal of heat from the catalyst by means of the products of the reaction is facilitated when these products are passed within and in heat exchange relation with the catalyst but not in direct contact therewith and preferably in a direction opposite to the direction of travel of the reacting gases. The gaseous prod.-

ucts leaving the cooler end the catalyst are thus permitted to absorb heat, particularly from that zone of the catalyst where the reaction is most active. If the zone where the gases first directly contact with the catalyst is at too low a temperature some heat may be given up by the gaseous products in this region before the gaseous products escape, t us tending to equalize the temperature of the several zones by heat distribution within the catal st. This may be understood more readily 'y reference to the zones as above mentioned. Since the gaseous products 'pass through the catalyst counter-current to the gases undergoing reaction, the returning products will not, because of the relatively slight temperature difference, absorb any material amount of heat from the third zone, but upon enteringrthe second zone, where the evolution of heat is relatively great, absorption will be accelerated and the temperature of the 'aseous products will rise accordingly. pon passing into the first zone, if t e reaction 1s not active there, a portion of the absorbed heat may be returned to the catal st until it is raised to a temperature at whic the reaction will proceed actively. Thereafter this zone would correspond to the second zone and heat would be actively absorbed hese and carried off in the gaseous products. The heat can be utilized, in any case, to raise the temperature of the cold gaseous mixture which is introduced to the apparatus, at the point where it may be delivered to the catalyst either with or without intermediate and further heating by heat exchange throlggh indirect contact with the catalyst. The nal temperature of the entering gases can be regulated by the application of heat from an external source as, for example, by the provision of a suitably arranged electric heatmg coil.

As an example of the type of apparatus which can be employed in carrying out the invention, the catalyst can be enclosed within a suitable receptacle which is in turn. disposed within a chamber surrounded by' a pressure-sustaining wall. The enterin gaseous mixture can be introduced throug a suitable inlet, preferably after heat exchange with the outgoing gaseous products. Conveniently, the entering gaseous mixture can be passed in heat exchanging relation either a out or through the catalyst before it is delivered thereto. For example, the gaseous mixture may travel in the s ace between the catalyst receptacle and t e pressure-sustaining wall and thence through tubes embedded in the catalyst or this arrangement may be reversed. When the gaseous mixture, preheated to the re uired temperature by heat exchange with t e catalyst as described, is delivered thereto the reaction commences and-the gaseous products are delivered from the catalyst at the opposite or cooler end thereof. At this int the gaseous mixture can be returned through one or more tubes embedded in the catalyst in heat exchange relation but not in direct contact therewith. The gaseous products thus pass throu h the successive zones of the catalyst an are discharged after absorbing surplus heat therefrom.

v A suitable ap aratus is illustrated in the accompanying cates a pressure-sustainin wall enclosi a chamber in which a cata yst receptacle is disposed. A body of catalyst C 1s placed within the receptacle B and a plurahty of tubes D are embedded therein and extend from one end, where they open into the space between the receptacle and the-pressure-sustaining wall to near the other end of the receptacle. The aseous mixture enters through an inlet and, after'passin about an outlet tube F, enters the space} whereit is in heat exchange relation with the catalyst. The gaseous mixture passes thence through the tubes D still in heat exchangin relation with the catalyst and is finally elivered to the catal st. The gaseous products enter the tube and return in heat exchanging relation with the catalyst, thereby absorbing heat in the zone of greatrawing, in which A indi-' mea re leased in the zone of greatest activity.

For the sake of convenience in temperature control the reaction ma he carrled out in such a way that the ten ency is for the incominggaseous mixture'to reach the catalyst at a temperature slightlyless than the lowestpermitting the active commencement of the reaction. The balance of the heat required may be imparted to the gases from an external source, for exam le, by means of an electrical heating coi'l It may be necessary to use such a coil either continuously or intermittently, depending upon the heat evolved in thereaction, the-radiation losses, the efliciency of heat exchange, etc.

While the apparatus as described is well I adapted for the accomplishment of the purpose of the invention, it should be understood that various modifications thereof are possible to permit the distribution and removal of heat in and from the catalyst and that various changes can he made in the apparatus and in the operation thereof as hereinbefore described without departing from the invention or sacrificing any of the advantages thereof.

I claim l. The method of efiecting catalytic exothermic gaseous reactions, which comprises introducing a gaseous mixture to the catalyst andpassing the gaseous poducts of the reaction through but not in direct contact with the catalyst.

2. The method of efiecting catalyticexothermic gaseous reactions under pressure,

which comprises passing a gaseous mixture over the catalyst and thereafter passing the gaseous products of the reaction in the opposite direction through but not in direct contact with the catalyst.

3. The method of efiecting catalytic exo-.

thermic gaseous reactions, which comprises introducing a gaseous mixture to the catalyst, passing the gaseous products of the reaction through but notin direct contact with the cata yst and thereafter passing-the gaseous products in heat exchange relation with the entering gaseous mixture.

4. The method of efiecting catalytic exothermic gaseous reactions under pressure, which comprises passing a gaseous mixture over the catalyst, thereafter passing the gaseous roducts of the reaction in the opposite direction through but not in direct contact with the catalyst and then passing" the gaseous products 1n heat exchange relation with the entering gaseous mixture.

5. The method of eifecting catalytic exothermic gaseous reactions, which comprises conveying a gaseous mixture .in heat exchange relation with the catalyst and thence into contact therewith and passing the gaseous products of the reactlon through but not in direct contactwith the catalyst.

6. The method of efiecting catalytic exothermic gaseous reactions under pressure, which comprises conveying a gaseous mixture in heat exchange relation with the catalyst and thence into contact therewith and thereafter passing the products of the reaction in the opposite direction through but not in direct contact with the catalyst.

7. The methodof effecting catalytic exothermic gaseous reactions, which comprises conveying a gaseous mixture in heat exchange relation with the catalyst and thence into contact therewith, passing the gaseous products of the reaction through but not exchange relation with the'entering gaseous mixture.

8. The method of eifecting catalytic exothermic gaseous reactions under pressure, which comprises conveying a gaseous mixture in heat exchange relation with the catalyst and thence into contact therewith, thereafter passing the products of the reaction in the opposite direction through but not in direct contact with the catalyst and then passing the gaseous products in heat exchange relation with the entering gaseous mixture.

9. The method of effecting the catalytic synthesis of ammonia under pressure, which comprises passing a gaseous mixture over the catalyst and thereafter passing the gaseous products of the reaction in the opposite direction through but not in direct contact with the catalyst.

10. The method of efi'ectin'g the catalytic synthesis of ammonia under pressure, which comprises introducing a gaseous mixture to the catalyst, passing the gaseous products of the reaction through but not in direct contact with the catalyst and thereafter passing the gaseous products in heat exchange relation with the entering gaseous mixture.

l1. Themethod of efiecting the catalytic synthesis of ammonia under pressure, which comprises passing a gaseous mixture over the catalyst, thereafter passing the gaseous products of the reaction in the opposite direction through but not in direct contact with the catalyst and then passing the gasthe entering gaseous mixture.

12. The method of effecting the catalytic synthesis of ammonia under pressure, which gaseous products of the reaction t rough but not in direct contact with the catalyst.

eous products in heat exchange relat -.on with 18. The method of effecting the catalytic synthesis of ammonia under pressure, which comprises convev ng a gaseous mixture in heat exchange relation with the catalyst and thence into contact therewith and thereafter passing the products of the reaction in the opposite direction through but not in direct contact with the catalyst.

14. The inethod of efiecting the catalytic synthesis of ammonia under pressure, which comprises couyl'gying a gaseous mixture in heat exchange ation with the catalyst and thence into contact therewith, assin the gaseous roducts of the reaction t roug but not in t contact with the catalyst and thereafter passing the gaseous products in heat exchange relation with the entering us mixture.

15. The method of efiecting the catalytic synthesis of ammonia under pressure, which comprises conve a aseous mixture in heat exchange re atlon with the catalyst and thence 1 into contact therewith, thereafter passing the products of thereaction in the opposite direction throu h but not in direct contact with the cata yst and then passthe gaseous products in heat exchange r efitionwith the entering aseous mixture.

16. In an apparatus for e ecting catalytic exothermic gaseous reactions under pressure, the combination of a pressure-sustaining wall, a catalyst receptacle therein and spaced from the wall to provide a passage for the entering gaseous mixture, means to sup 1]! a gaseous mixture to the space and to d; 'ver it to the catalyst and means connected to an outlet for the gases and embedded in the catalyst to direct the gaseous glroducts of the reaction through but not in rect contact with the catalyst.

17. In an apparatus for effecting catalytic exothermic gaseous reactions under pressure, the combination of a pressure-sustaining wall, a catalyst receptacle therein and ?)aced from the wall to provide a passage or the entering gaseous mitxure, means to suppl a gaseous mixture to the space and to e 'ver it to the catalyst anda tube embedded in the catalyst and connected to an outlet for the gases to direct the gaseous products of the reaction through but not in direct contact with the catalyst.

18. In an apparatus for effecting catalytic exothermic gaseous reactions under pressure, the combination of a -pressure-sus- Wall, a catalyst receptacle therein and spaced from the wall to provide a passage for the entering gaseous mixture, means to supply a gaseous mixture to'the space and to deliver it to the catalyst, means to direct the gaseous products of the reaction through but not in direct contact with the catalyst and means connected to an outlet for the gases and embedded in the catalyst to'permit heat exchange between the productsof the reaction and the entering gaseous mixture.

19. In an apparatus for effecting catalytic exothermic gaseous reactions under pressure, the combination of a pressure-sustaini wall, a catalyst receptacle therein and space the catalyst and connected to an outlet for the gases to direct the gaseous products of the reaction throu h but not in direct contact with the cata yst and means to permit heat exchan e between the products of the reaction am? the entering gaseous mixture.

20. In an apparatus for effecting catalytic exothermic gaseous reactions under pressure, the combination of a ressure-sustaining wall, a catalyst receptac e therein, means for passing the gases to react through but not In direct contact with the catalyst prior to actual contact therewith and means for passing the gaseous products of the reacttion through but not in direct contact with the catalyst.

21. In an apparatus for effecting catalytic exothermic gaseous reactions under pressure, the combination of a pressure-sustaining wall, a catalyst receptacle therein, a conduit embedded within the catal st and provided with an opening adapted to lead the gases into direct contact with the catalyst, and a second conduit embedded within the catalyst with an opening adapted to lead the gaseous roducts of the reaction through but not in 'rect contact with the catalyst, said openings being disposed at opposite ends 0 said catalyst receptacle.

22. In an apparatus for effecting catalytic exothermic gaseous reactions, a catalyst receptacle with an entrance conduit for the gases extending through a major portion of the catalyst and an exit conduit extending in the optposi'te direction through a major portion 0 the catalyst.

23. In an apparatus for efi'ecting catalytic exothermic gaseous reactions, the combination of a catalyst receptacle, a catalyst therein and conduits embedded in the. catalyst and connected respectively to the inlet and outlet for gases entering and leaving the 7 catalyst receptacle, the conduits 'communicating with the interior of the catalyst rece tacle at opposite ends thereof.

n testimony whereof I aifix 1n si ature.

ROGER WI LI MS.

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